Polymers of high molecular weight and process of producing same



Patented June 11, 1940 v UNITED STATES POLYMERS OF HIGH MOLECULAR WEIGHT AND PROCESS OF PRODUCING SAME Martin Mueller-Cunradi, Ludwigshafen-on-the- Rhine, and Michael Otto, Oppau, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany No Drawing.

.6 Claims.

The present invention relates to' improved polymers of high molecular weight and more spe- V Zpheric or elevated temperatures. These materials are non-viscous, limpid liquids and are useful for gasoline, but even the heaviest of this a type do not possess suflicient viscosity to be use- ,ful as lubricants. Iso-olefins have likewise been polymerized to materials of medium" molecular weight, for example to molecular weights fromv about 1,000 to 25,000 or thereabout, which materials are thick, viscous liquids with decided lubricating qualities. While they are very viscous, they are still to be classed as liquids. Such materials have been made by polymerizing the iso- I oleflns. isobutylene in particular, with catalysts,- of the type of aluminum chloride and boron fluoride while maintaining the reaction mixture at a temperature below -.10 C.

It has now been found that products of considerably higher molecular weight can be produced from iso-olefins,.especially fromisobutylene. These materials range in molecular weight from about 27,500 to 200,000 or 250,000 and even higher.. 7 Themolecular weight limit of 27,500 is critical as will be shown in the examples below.

While some of these materials exhibit cold flow,

they are definitely out of the liquid range and are solid in character because they show considerable' resistance to distortion under pressure, which is the primary distinction between liquid and solid, the former being relatively easily deformed. They are plastic and elastic and may be termed rubber-like in that sense although theyv do not resemble rubber chemically; that is, they are substantially fully'saturated while rubber is highly oleflnic and they are remarkably resistant to oxidation at low temperatures while rubber is ,not.;

These high molecular weight solid polymers are made from iso-oleflns, inparticular from is'obutylene, by polymerization with catalysts of the -Priedel-Crafts' type such as aluminum chloride,

ppli cation June 1, 1937, Serlal No. 14l5,828

zinc chloride, ferric chloride and titanium fluoride, but the readily volatilizable members of the group'are .by far the most desirable, especially boron fluoride which is normally gaseous.

terials, itis netessary to .operate at low temperatures; for example below 30 C. and preferably at much lower temperatures, for example '60 or C., and to maintain this low temperature during" the entire course of the reaction. The generation of heat during polymerization is considerable and if special care is not taken to rapidly absorb the heat, the temperature is found to rise rapidly and to prevent the formation of the higher polymers. Another important and essential feature in obtaining these high molecular weight polymers is to conduct the polymerization with highly purified raw materials: The presence of even minute amounts of certain materials in some way'inhibits polymerization so that low molecular weights are obtained. The presence of saturated hydrocarbons is not objectionable and it is usually desirable to work in the presence of such material to act as a solvent.

The most objectionable -materials which are likely to be foundin the raw material have been identified as sulfur compounds and oxygen derivatives of hydrocarbons such as alcohols, alder hydes, organic acids and the like, and the greatest care should be used to reduce the amounts of such materials to the lowest possible proportion. Alkyl halides are also likely to occur if, the sol-,

vent is re-used and care should be taken to reduce such material to the merest traces. Olefins of less than 4 carbon atoms are not found to be objectionable, ethylene and propylene not at all and butylenes only if present in proportions materially above say, 10 or 15%. If the operation is carried out at very "low temperaturesof the order of more objectionable and should be removed. The

'greaterthe number of carbon at'o'msinthe'olefin,

=the more objectionable they appear to be. In addition to these compounds may also be included aromatics such as benzol, toluol and the like.

Iso-oleflns arevobtained from several different sources;- first, from the cracked gases obtained from petroleum. Such, materials are-apt to contain, in addition to other oleflns relatively small In order to obtain these high molecular weight maamounts of sulfur in various forms. The iso oleflns may also be obtained as by-products of methanol synthesis. The'material obtained from this source is aptto contain other oleflns and f as n purified isobutylene and in this case a liquid small amounts of oxygen-containing materials. Iso-butane or other iso-paraflins may 'be dehydrogenated by well known means to. produce the iso-olefins and besides the other impurities, such polymers which must. be largely removed. It will be understood'that theparticular purification process must to some extent dependon the source of the raw materials. Impurities of higher or lower molecular weight can beseparated by distillation, but it must be carried out under careful conditions.

Sulfur compounds may beremoved in a variety of ways, depending on the particular type of sulfur. Mercaptans, for example, are ordinarily re moved by washing with caustic soda cr'other alkalis and hydrogen sulfideis removed in the same manner. Disulfldes which are not amenable to such treatment may be removedby treatment with heavy-inetals such as copper or copper oxide and the material can then be treatedwith soda or other suitable agent to remove the hydrogen sulflde produced. The. raw material may also 'be subjected, to hydrogenation under well known conditions under which the sulfur compound is converted into hydrogen sulfide which can be removed in the usual way. There is usuallysome 'loss of iso-olefin during hydrogenation but conditions are known under which the' removal of sulfur can be effected to a high degree without too greata' loss of the iso-olefln. Oxygen-containing materials such as the alcohols are best removed by careful distillation although it may be necessary in some instances to redistill several impurities are reduced to the merest traces. It is sometimes advantageous to continue the purification treatments for example to carefully distill over caustic soda or alcoholic soda so as to remove-most of the sulfur and separate higher and lower boiling impurities in a single operation.

' The purification method will therefore be a combinationof any of the above methods depending-on the particular impurities found in the =material. As mentioned above, it is usually deence of an inert solvent and it is found that alkyl fluorides and other halides are often found in the recirculated solvent. These may be removed by careful distillation, but preferably by the action same polymerization procedure was used, it was found that as little as .15% of a mercaptan (B. P. 0.) when added to a purified sample of isobutylene gave a liquid polymer having azmolecular weight of 5,000 when the same sample under the same conditions but to which no impurity had been added gave a solid polymer of high molecular weight. When .05% of the same mercaptan In a third instance 15% of-ethyl thioether was added to a highly a product is apt to contain iso or normal olefin times in orderto, produce a material in which the sirable to conduct the polymerization in the preswas added to the purified isobutylene a liquid polymer'with a molecular weight of 12,500 was ob .,,,Htain e d on polymerization.

.mer witha molecular weight of aooawas produced. The amount of alcohols that can be tolerated'is slightly more. than the above, for example .5 ,to. 1.0%, although it'is desirable to re-.

duce-the amount below thisquantity. In the case of the alkyl fluorides, the presence of 1% basedon the isobutylene caused a' very large,,reductionin molecular weight and even as little as .2% gave a marked decrease in molecular weight. These amounts are significant only atthe particular temperatures and; conditions employed and cannot be taken as absolute because at rela- ,tively lower-temperatures larger amounts of poison can be tolerated. v

The highest degree of purification is' acco plished by'converting theisobutylene into some other chemical substance which may be purified and then reconverted to isobutylene. As one instance of this the isobutylene may be polymerized for example with to 10% sulfuric acid at.

low temperatureand then heated to about 100 C. to effect polymerization, which produces di and triisobutylene without affecting other olefins.

This polymer is. then separated by distilling off impurities and unpolymerizedmaterial, then depolymerizing-the isobutylene polymer either by heat alone or bycracking catalysts such as clay.

alysts suitable for. the purpose. .Such'methods all solid pitches, tars and asphalts. The molecular weights can be controlled quite accurately byhighly purifying the raw-material and adjustmg the temperature under which polymerization is obtained. With the same stock, the lower the temperature the higher will be the molecular weight .obtained. The solid polymers may be milled and mixed with other materials in this way. They may be out with a sharp knife and are found to have measurable tensile strengths at room temperatures. They also show marked resistance to deformation under pressure. The lower. molecular weight materials, in the. range from 27,500 to 50,000 have lower tensile strengths than the materials above 60,000 and also less resistance to deformation under compression. Above this latter flgure'there does not appear to bemuch change in the property. These products are freely soluble in aliphatic hydrocarbons such as gasoline,- kerosene, gas oils and lubricating oils. 1 They are also soluble in aromatic solvents such as benzol and toluol, although they do not appear aliphatic hydrocarbon solvents. They are prevcipitated from the-solutions on the addition of a lower. molecular weight oxygen containing solvents such as ethyl or methyl alcohols, acetone and the like, Y

Example I In order to demonstrate the critical molecular weight at which the polymers of isobutylene become solid, a series ofdiilerent' molecular weight polymers ranging from 15,000. to 60,000 were prepared. l

to hem readily soluble inthese materials as in the 5 gr. samples of these were placed between polished-brass plates in a 6" x 6" Carver press directly proportional to the molecular weight but 7 is very small. In plotting the-two curves there was found to be a sharp breakat a molecular weight of 27,500.

Example II In a second series of tests to determine the same point A. S. T. M. penetrations (room temperature) were taken on a series of polymers ranging from 10,000 to 60,000 molecular weights. The load on the pin was 0 gr.

Molecular weight Penetration Averagi- These data when plotted show a sharp break at In a third series of tests the load in the pin was 50 gr. and'the data were collected as before:

When the data hithe above table are plotted, there is found to be a sharp break at 27,500.

Example III Isobutylene was produced from an isobutyl alcohol-by passing the same over aluminum oxide at 400 C. The isobutylene was condensed and carefully redistilled under pressure. This highly purified material was then polymerized at -80 0., the temperature being maintained throughout the reaction by the direct addition of solid carbon dioxide. The product obtained was a clear, colorless s'olid having plastic and elastic properties. It had a molecular weight of 40,000 according to the Staudinger method.

Example Ill This product was then polymerized at 73 F. by means of boron fluoride cooled by solid carbon j dioxide and yielded a polymer amounting to 57% of the original isobutane or 63.5% of the isobutylene. ,This polymer had a molecular weight of 23,000 (Staudinger).

In a similar run in which the dehydrogenation product was carefully distilled to 540% bottoms over alcoholic caustic potash. the yield of polymer clear.

was about the same but it had a molecular weight of 43,000.

In a similar run using the same polymerization technique but at a temperature of :-103 C. the

polymer had a molecular weight of 58,000.

Ezampla'V heated for a short time, approximately 1 minute to 110 C. then cooled and settled at 40 to 50 C. An oilylayer consisting of 65% isobutylene dimer and 35% trimer was withdrawn and carefully fractionated to segregate the dimer cut (98-120 C.) and the trimer (150-180 C.)

The latter cut is passed over a clay catalyst at at 800-850 F. and the product cooled, condensed,

revaporized by heating to'110 F., cooled slightly to condense heavy ends, ,washed with soda, and

finally with sodium plumbite solution. The product is then redistilled under a. high reflux ratio say 7 to 1 and this may be done over caustic soda for best results and the isobutylene is now ready for polymerization.

' Ethylene is carefully scrubbed with sulfuric, acid to remove ethyl ether, compressed and liquefied. Two gallons of liquefied isobutylene precooled to '78 C. are fed to a 10 gallon reactor and to this two gallons of the liquefied ethylene are added. To a separate two gallons of liquefied ethylene, boron fluorideis added through a capillary tube under 2 inches mercury pressure for one or two minutes. Then this mixture of ethylene and boron fluoride is added to the reactor whereupon a vigorous reaction occurs and a large volume of gas is liberated and 'l to 8 pounds of the high molecular weight product remain in the reactor. It has amolecular weight of 150,000 (staudinger).

Example VI Crude butylene out such as used in the prior example is carefully heated with 60-65% sulfuric acid at about 20 C. The product is settled and the acid layer is diluted with one and one-half times its'volume of water and carefully distilled. A constant boiling mixture containing tertiary butyl alcoholand 10% water is obtained at 795 C.' v

The product so obtained is dried with anhydrous potassium carbonate and refractionated, then dehydrated by refluxing with an equal volume of 40% phosphoric acid. Thisis preferred to sul furic acid because the latter introduces small amounts of sulfur.

The isobutylene is washed with water to remove traces of alcohol and is again dried. It is now ready for polymerization. To one volume of liquid isobutylene is added 1 volume of liquid ethylene prepared as in the previous example. An-

other volume of ethylene is treated with BF: as

described in the prior example and this mixture .is now added to the mixture of isobutylene and ethylene. An instantaneous. reaction occurs giving about yield of a. polymer having a molecular weight of 280,000 Staudinger. It is nearly white, rubber-like and contains much dissolved use. when thisris removed it is colorless, and

The present invention is not to be limited to any theory of the method of polymerization, nor to any particular method for purifying or preparing the isobutylene, but only tothe followlng claims in which it is desired to claim all novelty inherent in the invention.

We claim:

1. An improved process for producing solid polymers of iso-olefins comprising preparing an iso-olefin in a condition of high purity such that sulfur its compounds, normal claims of more than 4 carbon atoms, alkyl halides oxygen contain ing derivatives of hydrocarbons and aromatic hy-' drocarbons are reduced to the meresttraces and then polymerizing the purified iso-olefin while maintaining a temperature below -30 0. throughout the reaction.

I 2. An improved process for producing solid elastic polymers of isobutylene comprising pre paring an isobutylene by reducing the amount of sulfur, its compounds, normal olefins of ,more than 4 carbon atoms, oxygen containing derivatives of hydrocarbons, alkyl halides and aromatic compounds to the merest traces and then polymerizing the highlypurified product with boronfluoride while maintaining a temperature below -30 C. throughout the reaction.

process of claim 1.

aaoaava 3. An iso-olefln polymer, beinga plastic and elastic rubber-like solid at ordinary temperatures, having a molecular weight above about 27,500, substantially colorless, soluble in hydro carbon solvents, insoluble -in methyl alcohol, ethyl alcohol and acetone and prepared by the 4; An isobutylene polymer, being a plastic and elastic rubber-like solid at ordinary tempera: tures, having, a molecular weight "above about 1 27,500, substantially colorless, soluble in hydro carbon solvents, insoluble in methyl alcohol,

ethyl alcohol and acetone and prepared by the process of claim 2. i 1

5. A process in accordance with claim Lin 5 which the purified iso-olefln is polymerized-in an inert solvent having the condition of high purity. a

6.'A process in accordance with claim 2, in

which the boron fluoride is added to liquefied ethylene of high purity before it isused to polymerize the highly purified lsobutylene in the presence of the liquefied ethylene.

MA'RTIN MUELLER-CUNRADl. MICHAEL o'rro. 

